Liquid detergent compositions containing brighteners and polymers for preventing fabric spotting

ABSTRACT

Compositions for reducing brightener spotting comprise a polymer selected from the group consisting of polyamine N-oxide containing polymers, N-vinylimidazole N-vinylpyrrolidone copolymers and mixtures thereof, a stilbene brightener, and from 5% to 7% hydrogen peroxide, wherein the weight ratio of the polymer to the brightener is from 1:20 to 20:1 and the pH of the composition is from 2 to 6.

TECHNICAL FIELD

The present invention relates to liquid detergent compositionscomprising optical brighteners. More in particular, the presentinvention relates to the use of polyamine N-oxide containing polymersand/or N-vinylimidazole N-vinylpyrrolidone copolymers in detergentcompositions containing brighteners for reducing fabric spottingassociated with the use of said brighteners.

BACKGROUND OF THE INVENTION

Optical brighteners, also known as fluorescent whitening agents, arecommonly used in liquid laundry additives. Brighteners deposit ontofabrics where they absorb ultraviolet radiant energy and reemit it asblue light.

This reduces or eliminates any yellowish cast to fabrics and gives thema bright appearance.

A specific problem associated with liquid detergent compositionscontaining brighteners is their undiluted application on textiles, onwhich high brightener concentration becomes visible as a whitener spot.

The present invention is based on the discovery that polyamine N-oxidecontaining polymers and/or N-vinylimidazole N-vinylpyrrolidonecopolymers inhibit the fabric spotting of brighteners. Said polymers areused to complex or absorb the fugitive dyes washed out of dyed fabricsbefore they have the opportunity to become attached to other articles inthe wash.

Copending EP Patent Application 92202168.8 describes dye transferinhibiting compositions comprising polyamine N-oxides containingpolymers. N-vinylimidazole N-vinylpyrrolidone copolymers are describedin prior art documents such as DE 2 814 287-A which relates to detergentcompositions comprising 0.1 to 10 wt % water-soluble orwater-dispersible N-vinyl imidazole homo- or copolymer in combinationwith anionic and/or nonionic surfactants and other detergentingredients. EP 372 291 relates to a process for washingdiscolouration-sensitive textiles. The wash liquor containsanionic/nonionic surfactants and watersoluble polymers e.g. (co)polymersN-vinylimidazole, N-vinyloxazolidone or N-vinylpyrrolidone. EP 327 927describes a granular detergent additive comprising water-solublepolymeric compounds based on N-vinylpyrrolidone and/or N-vinylimidazoleand/or N-vinyloxazolidone and cationic compounds. DE 4027832-A discloseselectrolyte-free liquid detergent compositions comprising zeolite A,nonionic surfactants and dye transfer inhibiting polymers. The dyetransfer inhibiting polymers are homo-and copolymers selected fromN-vinylpyrrolidone and/or N-vinylimidazole and/or N-vinyloxazolidone.

According to the present invention, a liquid detergent compositioncomprising a brightener is provided which reduces or eliminates thefabric spotting of brighteners upon pretreatment.

SUMMARY OF THE INVENTION

The present invention relates to the use of a polyamine N-oxidecontaining polymers and/or N-vinylimidazole N-vinylpyrrolidonecopolymers in liquid detergent compositions for inhibiting fabricspotting associated with detergent compositions containing brighteners.

DETAILED DESCRIPTION OF THE INVENTION

The compositions of the present invention comprise as essential elementsa brightener and a polymer selected from polyamine N-oxide containingpolymers and/or N-vinylimidazole N-vinylpyrrolidone copolymers.

(a) Polyamine N-oxide containing polymers

The compositions of the present invention comprise as an essentialelement a polymer selected from polyamine N-oxide containing polymerswhich contain units having the following structure formula: ##STR1##wherein P is a polymerisable unit, whereto the N--O group can beattached to or wherein

the N--O group forms part of the polymerisable unit or a combination ofboth. ##STR2## R are aliphatic, ethoxylated aliphatics, aromatic,heterocyclic or alicyclic groups or any combination thereof whereto thenitrogen of the N--O group can be attached or wherein the nitrogen ofthe N--O group is part of these groups.

The N--O group can be represented by the following general structures##STR3## wherein R1, R2, and R3 are aliphatic groups, aromatic,heterocyclic or alicyclic groups or combinations thereof, x or/and yor/and z is 0 or 1 and wherein the nitrogen of the N--O group can beattached or wherein the nitrogen of the N--O group forms part of thesegroups.

The N--O group can be part of the polymerisable unit (P) or can beattached to the polymeric backbone or a combination of both.

Suitable polyamine N-oxides wherein the N--O group forms part of thepolymerisable unit comprise polyamine N-oxide containing polymerswherein R is selected from aliphatic, aromatic, alicyclic orheterocyclic groups.

One class of said polyamine N-oxide containing polymers comprises thegroup of polyamine N-oxides wherein the nitrogen of the N--O group formspart of the R-group. Preferred polyamine N-oxide containing polymers arethose wherein R is a heterocyclic group such as pyridine, pyrrole,imidazole, pyrrolidine, piperidine, quinoline, acridine and derivativesthereof.

Another class of said polyamine N-oxide containing polymers comprisesthe group of polyamine N-oxides wherein the nitrogen of the N--O groupis attached to the R-group.

Other suitable polyamine N-oxides are the polyamine oxides whereto theN--O group is attached to the polymerisable unit.

Preferred class of these polyamine N-oxides are the polyamine N-oxideshaving the general formula (I) wherein R is an aromatic, heterocyclic oralicyclic groups wherein the nitrogen of the N--O functional group ispart of said R group. Examples of these classes are polyamine oxideswherein R is a heterocyclic compound such as pyridine, pyrrole,imidazole and derivatives thereof.

Another preferred class of polyamine N-oxides are the polyamine N-oxidecontaining polymers having the general formula (I) wherein R arearomatic, heterocyclic or alicyclic groups wherein the nitrogen of theN--O functional group is attached to said R groups. Examples of theseclasses are polyamine oxides wherein R groups can be aromatic such asphenyl.

Any polymer backbone can be used as long as the amine oxide polymerformed is water-soluble and has dye transfer inhibiting properties.Examples of suitable polymeric backbones are polyvinyls, polyalkylenes,polyesters, polyethers, polyamide, polyimides, polyacrylates andmixtures thereof.

The amine N-oxide polymers of the present invention typically have aratio of amine to the amine N-oxide of 10:1 to 1:1000000. However theamount of amine oxide groups present in the polyamine oxide containingpolymer can be varied by appropriate copolymerization or by appropriatedegree of N-oxidation. Preferably, the ratio of amine to amine N-oxideis from 2:3 to 1:1000000. More preferably from 1:4 to 1:1000000, mostpreferably from 1:7 to 1:1000000. The polymers of the present inventionactually encompass random or block copolymers where one monomer type isan amine N-oxide and the other monomer type is either an amine N-oxideor not. The amine oxide unit of the polyamine N-oxides has a PKa<10,preferably PKa<7, more preferred PKa<6.

The polyamine N-oxide containing polymers can be obtained in almost anydegree of polymerisation. The degree of polymerisation is not criticalprovided the material has the desired water-solubility anddye-suspending power.

Typically, the average molecular weight is within the range of 500 to1000,000; preferably from 1,000 to 50,000, more preferably from 2,000 to30,000, most preferably from 3,000 to 20,000.

The polyamine N-oxide containing polymers of the present invention aretypically present from 0.001 to 10%, more preferably from 0.01 to 2%,most preferred from 0.05 to 1% by weight of the dye transfer inhibitingcomposition.

The present compositions are conveniently used as additives toconventional detergent compositions for use in laundry operations. Thepresent invention also encompasses dye transfer inhibiting compositionswhich will contain detergent ingredients and thus serve as detergentcompositions.

Methods for making polyamine N-oxides

The production of the polyamine-N-oxides may be accomplished bypolymerizing the amine monomer and oxidizing the resultant polymer witha suitable oxidizing agent, or the amine oxide monomer may itself bepolymerized to obtain the polyamine N-oxide. The synthesis of polyamineN-oxide can be exemplified by the synthesis of polyvinylpyrridineN-oxide.

Poly-4-vinylpyridine ex Polysciences (mw. 50 000, 5.0 g., 0.0475 mole)was predisolved in 50 ml acetic acid and treated with a peracetic acidsolution (25 g of glacial acetic acid, 6.4 g of a 30% vol. solution ofH₂ O₂, and a few drops of H₂ SO₄ give 0.0523 mols of peracetic acid) viaa pipette. The mixture was stirred over 30 minutes at ambienttemperature (32 C.). The mixture was then heated to 80-85 C. using anoil bath for 3 hours before allowing to stand overnight. The polymersolution then obtained is mixed with 11 of acetone under agitation. Theresulting yellow brown viscous syrup formed on the bottom is washedagain with 11 of aceton to yield a pale crystalline solid.

The solid was filtered off by gravity, washed with acetone and thendried over P₂ O₅.

The amine: amine N-oxide ratio of this polymer is 1:4.

The N-vinylimidazole N-vinylpyrrolidone copolymer

The present invention comprises as an essential detergent ingredient apolymer selected from the N-vinylimidazole N-vinylpyrrolidonecopolymers.

The N-vinylimidazole N-vinylpyrrolidone polymers have an averagemolecular weight range from 5000-1,000,000, preferably from 20000-200,000.

Highly preferred polymers for use in detergent compositions according tothe present invention comprise a polymer selected from N-vinylimidazoleN-vinylpyrrolidone copolymers wherein said polymer has an averagemolecular weight range from 5,000 to 50,000 more preferably from 8,000to 30,000, most preferably from 10,000 to 20,000.

The average molecular weight range was determined by light scattering asdescribed in Barth H. G. and Mays J. W. Chemical Analysis Vol.113."Modern Methods of Polymer Characterization.

Preferred N-vinylimidazole N-vinylpyrrolidone copolymers have an averagemolecular weight range from 5,000 to 50,000, more preferably from 8,000to 30,000, most preferably from 10,000 to 20,000.

The N-vinylimidazole N-vinylpyrrolidone copolymers characterized byhaving said average molecular weight range provide excellent dyetransfer inhibiting properties while not adversely affecting thecleaning performance of detergent compositions formulated therewith.

The N-vinylimidazole N-vinylpyrrolidone copolymer of the presentinvention has a molar ratio of N-vinylimidazole to N-vinylpyrrolidonefrom 1:1 to 0.2:1, more preferably from 0.8:1 to 0.3:1, most preferablyfrom 0.6:1 to 0.4:1.

The N-vinylimidazole N-vinylpyrrolidone copolymers can be lineair orbranched. The level of the N-vinylimidazole N-vinylpyrrolidone presentin the detergent compositions is from 0.01 to 10%, more preferably from0.05 to 5%, most preferably from 0.1 to 1% by weight of the detergentcomposition.

(b) Brightener

An essential ingredient of the compositions according to the presentinvention is a brightener. Suitable brighteners include stilbenebrighteners. Stilbene brighteners are aromatic compounds with two arylgroups separated by an alkene chain. They preferably have the followingstructural formula: ##STR4## wherein R₁ is hydrogen, halogen, alkyl,alkoxy or phenyl; R₂ is hydrogen or alkyl;

M is hydrogen, an alkali metal or ammonium ion;

n=0-2, but the formula must contain at least one SO₃ M group; and

m=1-2 and when m=1, the substituent on the linkage carbon is hydrogen.

Especially suitable stilbene brighteners for use herein are described inU.S. Pat. Nos. 4,309,316, 4,298,490 and 5,035,825.

Bleach-stable anionic brighteners with sulfonic acid group(s) which workon cotton (cellulosics) are preferred.

The most preferred stilbene brighteners for use herein, because it isbleach-stable, is Tinopal^(R) CBS-X, which is benzenesulfonic acid,2,2'-((1,1'-biphenyl)-4,4'-diyldi-2,1-ethenediyl)bis-, disodium salt (CAIndex Name). The formula for Tinopal^(R) CBS-X is ##STR5## Otherbrighteners that can be used are hydrophobic having the formula:##STR6## wherein R₁, R₂, R₃ and R₄ represent, selected independently,anilino, cyclohexylamino, piperazino, phenylenediamino, toluenediamino,morpholino, and aminophenol, with the proviso that the brightenercontains not more than one morpholino group.

Suitable brightener species include any combination of the possible R₁₋₄moieties. Examples of preferred brightener species are thetetra-anilino, tetra-piperazino, tetra-cyclohexylamino and combinationsthereof such as for example the di-anilinodipiperazino; and thedianilino-dicyclohexylamino species.

Highly preferred for reasons of minimizing brightener staining are thetetraanilio derivatives, having the following formula:

4,4'-bis (4-anilino-6-anilino-s-triazin-2-yl)amino)-2,2'-stilbenedisulfonic acid sodium salt (A). A preferred brightener system in thecontext of this invention contains at least 40% (by reference to thetotal amount of the detergent brightener) of the specific hydrophobicbrightener referred to hereinbefore in combination with a conventionaldetergent brightener, e.g., a di-sulfonated dianilino, dimorpholinostilbene brightener.

Conventional detergent brighteners for use in combination with thehydrophobic species described hereinabove embrace common detergentbrighteners inclusives of:

    4,4(2H-naphtho(1,2-d)triazol-2-yl)-2-stilbenesulfonic acid, sodium salt;(i)

    4,4'-Bis((4-anilino-6(N-2-hydroxyethyl-N-methylamino)-s-triazin-2yl) amino)-2,2'stilbenedisulfonic acid disodium salt;         (ii)

    4,4'-bis((4-anilino-6-morpholino-s-trizain-2-yl)amino)-2,2'-stilbenedisulfonic acid, sodium salt;                                     (iii)

    2,2-(4,4'-biphenylene divinylene)-dibenzenesulfonic acid, disodium salt;(ivi)

    4,4'-bis(4-phenyl-2H-1,2,3-triazol-2-yl)disodium salt      (vi)

4,4'-bis(4-anilino-6-morpholino-1,3,5-triazin-2-yl)amino)-2-stilbenesulfonate sodium salt.

The weight ratio of polyamine N-oxide containing polymer and/orN-vinylimidazole N-vinylpyrrolidone to the brightener present in thedetergent composition is from 1/20 to 20/1, preferably from 1/10 to12/1, more preferably from 2/1 to 7/1.

Detergent ingredients

In another embodiment of the present invention, a liquid detergentcomposition is provided comprising the dye transfer inhibitingcomposition mixed with detergent ingredients. A wide range ofsurfactants can be used in the detergent composition of the presentinvention.

A typical listing of anionic, nonionic, ampholytic and zwitterionicclasses, and species of these surfactants, is given in U.S. Pat. No.3,664,961 issued to Norris on May 23, 1972.

Preferred anionic surfactants include the alkyl sulfate surfactantshereof which are water soluble salts or acids of the formula ROSO₃ Mwherein R preferably is a C₁₀ -C₂₄ hydrocarbyl, preferably an alkyl orhydroxyalkyl having a C₁₀ -C₂₀ alkyl component, more preferably a C₁₂-C₁₈ alkyl or hydroxyalkyl, and M is H or a cation, e.g., an alkalimetal cation (e.g. sodium, potassium, lithium), or ammonium orsubstituted ammonium (e.g. methyl-, dimethyl-, and trimethyl ammoniumcations and quaternary ammonium cations such as tetramethyl-ammonium anddimethyl piperdinium cations and quaternary ammonium cations derivedfrom alkylamines such as ethylamine, diethylamine, triethylamine, andmixtures thereof, and the like). Typically, alkyl chains of C₁₂ -C₁₆ arepreferred for lower wash temperatures (e.g. below about 50° C.) andC_(16-C) ₁₈ alkyl chains are preferred for higher wash temperatures(e.g. above about 50° C.).

Highly preferred anionic surfactants include alkyl alkoxylated sulfatesurfactants hereof are water soluble salts or acids of the formulaRO(A)_(m) SO3M wherein R is an unsubstituted C₁₀ -C₂₄ alkyl orhydroxyalkyl group having a C₁₀ -C₂₄ alkyl component, preferably a C₁₂-C₂₀ alkyl or hydroxyalkyl, more preferably C₁₂ -C₁₈ alkyl orhydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero,typically between about 0.5 and about 6, more preferably between about0.5 and about 3, and M is H or a cation which can be, for example, ametal cation (e.g., sodium, potassium, lithium, calcium, magnesium,etc.), ammonium or substituted-ammonium cation. Alkyl ethoxylatedsulfates as well as alkyl propoxylated sulfates are contemplated herein.Specific examples of substituted ammonium cations include methyl-,dimethyl, trimethyl-ammonium cations and quaternary ammonium cationssuch as tetramethyl-ammonium and dimethyl piperdinium cations and thosederived from alkylamines such as ethylamine, diethylamine,triethylamine, mixtures thereof, and the like. Exemplary surfactants areC₁₂ -C₁₈ alkyl polyethoxylate (1.0) sulfate (C₁₂ -C₁₈ E(1.0)M), C₁₂ -C₁₈alkyl polyethoxylate (2.25) sulfate (C₁₂ -C₁₈ E(2.25)M), C₁₂ -C₁₈ alkylpolyethoxylate (3.0) sulfate (C₁₂ -C₁₈ E(3.0)M), and C₁₂ -C₁₈ alkylpolyethoxylate (4.0) sulfate (C₁₂ -C₁₈ E(4.0)M), wherein M isconveniently selected from sodium and potassium.

Other suitable anionic surfactants to be used are alkyl ester sulfonatesurfactants including linear esters of C₈ -C₂₀ carboxylic acids (i.e.,fatty acids) which are sulfonated with gaseous SO₃ according to "TheJournal of the American Oil Chemists Society", 52 (1975), pp. 323-329.Suitable starting materials would include natural fatty substances asderived from tallow, palm oil, etc.

The preferred alkyl ester sulfonate surfactant, especially for laundryapplications, comprise alkyl ester sulfonate surfactants of thestructural formula: ##STR7## wherein R³ is a C₈ -C₂₀ hydrocarbyl,preferably an alkyl, or combination thereof, R⁴ is a C₁ -C₆ hydrocarbyl,preferably an alkyl, or combination thereof, and M is a cation whichforms a water soluble salt with the alkyl ester sulfonate. Suitablesalt-forming cations include metals such as sodium, potassium, andlithium, and substituted or unsubstituted ammonium cations, such asmonoethanolamine, diethanolamine, and triethanolamine. Preferably, R³ isC₁₀ -C₁₆ alkyl, and R⁴ is methyl, ethyl or isopropyl. Especiallypreferred are the methyl ester sulfonates wherein R³ is C₁₀ -C₁₆ alkyl.

Other anionic surfactants useful for detersive purposes can also beincluded in the laundry detergent compositions of the present invention.These can include salts (including, for example, sodium, potassium,ammonium, and substituted ammonium salts such as mono-, di-andtriethanolamine salts) of soap, C₉ -C₂₀ linear alkylbenzenesulfonates,C₈ -C₂₂ primary of secondary alkanesulfonates, C₈ -C₂₄ olefinsulfonates,sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzedproduct of alkaline earth metal citrates, e.g., as described in Britishpatent specification No. 1,082,179, C₈ -C₂₄ alkylpolyglycolethersulfates(containing up to 10 moles of ethylene oxide); alkyl glycerolsulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerolsulfates, alkyl phenol ethylene oxide ether sulfates, paraffinsulfonates, alkyl phosphates, isethionates such as the acylisethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates,monoesters of sulfosuccinates (especially saturated and unsaturated C₁₂-C₁₈ monoesters) and diesters of sulfosuccinates (especially saturatedand unsaturated C₆ -C₁₂ diesters), acyl sarcosinates, sulfates ofalkylpolysaccharides such as the sulfates of alkylpolyglucoside (thenonionic nonsulfated compounds being described below), branched primaryalkyl sulfates, and alkyl polyethoxy carboxylates such as those of theformula RO(CH₂ CH₂ O)_(k) --CH₂ COO--M+ wherein R is a C₈ -C₂₂ alkyl, kis an integer from 0 to 10, and M is a soluble salt-forming cation.Resin acids and hydrogenated resin acids are also suitable, such asrosin, hydrogenated rosin, and resin acids and hydrogenated resin acidspresent in or derived from tall oil. Further examples are described in"Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perryand Berch). A variety of such surfactants are also generally disclosedin U.S. Pat. No. 3,929,678, issued Dec. 30, 1975 to Laughlin, et al. atColumn 23, line 58 through Column 29, line 23 (herein incorporated byreference).

When included therein, the laundry detergent compositions of the presentinvention typically comprise from about 0.2% to about 40%, preferablyfrom about 0.5% to about 20% by weight of such anionic surfactants.

One class of nonionic surfactants useful in the present invention arecondensates of ethylene oxide with a hydrophobic moiety to provide asurfactant having an average hydrophilic-lipophilic balance (HLB) in therange from 6 to 17, preferably from 8 to 17, more preferably from 9.5 to14, most preferably from 12 to 14. The hydrophobic (lipophilic) moietymay be aliphatic or aromatic in nature and the length of thepolyoxyethylene group which is condensed with any particular hydrophobicgroup can be readily adjusted to yield a water-soluble compound havingthe desired degree of balance between hydrophilic and hydrophobicelements.

Preferred nonionic surfactants include C9-C13 primary alcoholethoxylates containing 3-30 moles of ethylene oxide per mole of alcohol.

Other nonionics that can be used are C13-C15 primary alcohol alkoxylatescontaining polyethoxy blocks comprising 1 to 2 ethoxy groups and alsocontaining polypropoxy blocks comprising 3 to 4 propoxy groups.

Especially preferred nonionic surfactants are the C₉ -C₁₅ primaryalcohol ethoxylates containing 3-12 moles of ethylene oxide per mole ofalcohol, particularly the C₁₂ -C₁₅ primary alcohols containing 5-8 molesof ethylene oxide per mole of alcohol.

Another class of nonionic surfactants comprises alkyl polyglucosidecompounds of general formula

    RO(C.sub.n H.sub.2n O).sub.t Z.sub.x

wherein Z is a moiety derived from glucose; R is a saturated hydrophobicalkyl group that contains from 12 to 18 carbon atoms; t is from 0 to 10and n is 2 or 3; x is from 1.3 to 4, the compounds including less than10% unreacted fatty alcohol and less than 50% short chain alkylpolyglucosides. Compounds of this type and their use in detergent aredisclosed in EP-B 0 070 077, 0 075 996 and 0 094 118.

Also suitable as nonionic surfactants are poly hydroxy fatty acid amidesurfactants of the formula ##STR8## wherein R¹ is H, or R¹ is C₁₋₄hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof, R²is C₅₋₃₁ hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linearhydrocarbyl chain with at least 3 hydroxyls directly connected to thechain, or an alkoxylated derivative thereof. Preferably, R¹ is methyl,R² is a straight C₁₁₋₁₅ alkyl or alkenyl chain such as coconut alkyl ormixtures thereof, and Z is derived from a reducing sugar such asglucose, fructose, maltose, lactose, in a reductive amination reaction.

When included therein, the laundry detergent compositions of the presentinvention typically comprise from about 0.5% to about 40%, preferablyfrom about 0.5% to about 20% by weight of such nonionic surfactans,highly preferred from 0.5% to 10%.

The compositions according to the present invention may further comprisea builder system. Any conventional builder system is suitable for useherein including aluminosilicate materials, silicates, polycarboxylatesand fatty acids, materials such as ethylenediamine tetraacetate, metalion sequestrants such as aminopolyphosphonates, particularlyethylenediamine tetramethylene phosphonic acid and diethylene triaminepentamethylenephosphonic acid. Though less preferred for obviousenvironmental reasons, phosphate builders can also be used herein.

Suitable builders can be an inorganic ion exchange material, commonly aninorganic hydrated aluminosilicate material, more particularly ahydrated synthetic zeolite such as hydrated zeolite A, X, B or HS.Another suitable inorganic builder material is layered silicate, e.g.SKS-6 (Hoechst). SKS-6 is a crystalline layered silicate consisting ofsodium silicate (Na₂ Si₂ O₅).

Suitable polycarboxylates builders for use herein include citric acid,preferably in the form of a water-soluble salt, derivatives of succinicacid of the formula R--CH(COOH)CH2(COOH) wherein R is C10-20 alkyl oralkenyl, preferably C12-16, or wherein R can be substituted withhydroxyl, sulfo sulfoxyl or sulfone substituents. Specific examplesinclude lauryl succinate, myristyl succinate, palmitylsuccinate2-dodecenylsuccinate, 2-tetradecenyl succinate. Succinatebuilders are preferably used in the form of their water-soluble salts,including sodium, potassium, ammonium and alkanolammonium salts.

Other suitable polycarboxylates are oxodisuccinates and mixtures oftartrate monosuccinic and tartrate disuccinic acid such as described inU.S. Pat. No. 4,663,071. Especially for the liquid execution herein,suitable fatty acid builders for use herein are saturated or unsaturatedC10-18 fatty acids, as well as the corresponding soaps. Preferredsaturated species have from 12 to 16 carbon atoms in the alkyl chain.The preferred unsaturated fatty acid is oleic acid. Another preferredbuilder system for liquid compositions is based on dodecenyl succinicacid.

Other suitable water-soluble organic salts are the homo- or co-polymericacids or their salts, in which the polycarboxylic acid comprises atleast two carboxyl radicals separated from each other by not more thantwo carbon atoms.

Polymers of this type are disclosed in GB-A-1,596,756. Examples of suchsalts are polyacrylates of MW 2000-5000 and their copolymers with maleicanhydride, such copolymers having a molecular weight of from 20,000 to70,000, especially about 40,000.

Detergency builder salts are normally included in amounts of from 2% to80% by weight of the composition preferably from 20% to 70% and mostusually from 30% to 60% by weight.

Detergent compositions according to the present invention may includebleaching agents. The bleaching agent suitable for the present inventioncan be an activated or non-activated bleaching agent.

One category of oxygen bleaching agent that can be used encompassespercarboxylic acid bleaching agents and salts thereof. Suitable examplesof this class of agents include magnesium monoperoxyphthalatehexahydrate, the magnesium salt of meta-chloro perbenzoic acid,4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid.Such bleaching agents are disclosed in U.S. Pat. No. 4,483,781, U.S.patent application Ser. No. 740,446, European Patent Application0,133,354 and U.S. Pat. No. 4,412,934. Highly preferred bleaching agentsalso include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S.Pat. No. 4,634,551.

Another category of bleaching agents that can be used encompasses thehalogen bleaching agents. Examples of hypohalite bleaching agents, forexample, include trichloro isocyanuric acid and the sodium and potassiumdichloroisocyanurates and N-chloro and N-bromo alkane sulphonamides.Such materials are normally added at 0.5-10% by weight of the finishedproduct, preferably 1-5% by weight.

Preferably, the bleaches suitable for the present invention includeperoxygen bleaches. Examples of suitable water-soluble solid peroxygenbleaches include hydrogen peroxide releasing agents such as perborates,e.g. perborate monohydrate, perborate tetrahydrate, persulfates,percarbonates, peroxydisulfates, perphosphates and peroxyhydrates.Preferred bleaches are percarbonates and perborates.

The hydrogen peroxide releasing agents can be used in combination withbleach activators such as tetraacetylethylenediamine (TAED),nonanoyloxybenzenesulfonate (NOBS, described in U.S. Pat. No.4,412,934), 3,5,-trimethylhexanoloxybenzenesulfonate (ISONOBS, describedin EP 120,591) or pentaacetylglucose (PAG), which are perhydrolyzed toform a peracid as the active bleaching species, leading to improvedbleaching effect. Also suitable activators are acylated citrate esters(ATC) such as disclosed in Copending European Patent Application No.91870207.7.

A preferred bleaching agent is hydrogen peroxide.

The hydrogen peroxide may be present as such or may be present by addingan enzymatic system (i.e. an enzyme and a substrate therefore) which iscapable of generating hydrogen peroxide at the beginning or during thewashing and/or rinsing process. Such enzymatic systems are disclosed inEP Patent Application 91202655.6 filed Oct. 9, 1991.

Other peroxygen bleaches suitable for the present invention includeorganic peroxyacids such as percarboxylic acids.

Bleaching agents other than oxygen bleaching agents are also known inthe art and can be utilized herein. One type of non-oxygen bleachingagent of particular interest includes photoactivated bleaching agentssuch as the sulfonated zinc and/or aluminum phthalocyanines. Thesematerials can be deposited upon the substrate during the washingprocess. Upon irradiation with light, in the presence of oxygen, such asby hanging clothes out to dry in the daylight, the sulfonated zincphthalocyanine is activated and, consequently, the substrate isbleached. Preferred zinc phthalocyanine and a photoactivated bleachingprocess are described in U.S. Pat. No. 4,033,718. Typically, detergentcompositions will contain about 0.0001% to about 1.25%, by weight, ofsulfonated zinc phthalocyanine. In addition, it has been found that thepolyamine-N-oxide containing polymers eliminate or reduce the depositionof said photoactivated bleaching agents onto fabrics resulting insubstantial no fabric spotting upon pretreatment and/or in the wash.

Other detergent ingredients that can be included are detersive enzymeswhich can be included in the detergent formulations for a wide varietyof purposes including removal of protein-based, carbohydrate-based, ortriglyceride-based stains, for example, and prevention of refugee dyetransfer. The enzymes to be incorporated include proteases, amylases,lipases, cellulases, and peroxidases, as well as mixtures thereof Othertypes of enzymes may also be included. They may be of any suitableorigin, such as vegetable, animal, bacterial, fungal and yeast origin.

Enzymes are normally incorporated at levels sufficient to provide up toabout 5 mg by weight, more typically about 0.05 mg to about 3 mg, ofactive enzyme per gram of the composition.

Suitable examples of proteases are the subtilisins which are obtainedfrom particular strains of B. subtilis and B. licheniforms. Proteolyticenzymes suitable for removing protein-based stains that are commerciallyavailable include those sold under the tradenames Alcalase, Savinase andEsperase by Novo Industries A/S (Denmark) and Maxatase by InternationalBio-Synthetics, Inc. (The Netherlands) and FN-base by Genencor, Optimaseand opticlean by MKC.

Of interest in the category of proteolytic enzymes, especially forliquid detergent compositions, are enzymes referred to herein asProtease A and Protease B. Protease A is described in European PatentApplication 130,756. Protease B is described in European PatentApplication Serial No. 87303761.8. Amylases include, for example,-amylases obtained from a special strain of B. licheniforms, describedin more detail in British Patent Specification No. 1,296,839 (Novo).Amylolytic proteins include, for example, Rapidase, Maxamyl(International Bio-Synthetics, Inc.) and Termamyl,(Novo Industries).

The cellulases usable in the present invention include both bacterial orfungal cellulase. Preferably, they will have a pH optimum of between 5and 9.5. Suitable cellulases are disclosed in U.S. Pat. No. 4,435,307,Barbesgoard et al, which discloses fungal cellulase produced fromHumicola insolens. Suitable cellulases are also disclosed inGB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832.

Examples of such cellulases are cellulases produced by a strain ofHumicola insolens (Humicola grisea var. thermoidea), particularly theHumicola strain DSM 1800, and cellulases produced by a fungus ofBacillus N or a cellulase 212-producing fungus belonging to the genusAeromonas, and cellulase extracted from the hepatopancreas of a marinemollusc (Dolabella Auricula Solander).

Other suitable cellulases are cellulases originated from HumicolaInsulins having a molecular weight of about 50 KDa, an isoelectric pointof 5.5 and containing 415 amino acids. Such cellulase are described inCopending European patent application No. 93200811.3, filed Mar. 19,1993.

Especially suitable cellulase are the cellulase having color carebenefits. Examples of such cellulases are cellulase described inEuropean patent application No. 91202879.2, filed Nov. 6, 1991 Carezyme(Novo).

Suitable lipase enzymes for detergent usage include those produced bymicroorganisms of the Pseudomonas group, such as Pseudomonas stutzeriATCC 19.154, as disclosed in British Patent 1,372,034. Suitable lipasesinclude those which show a positive immunoligical cross-reaction withthe antibody of the lipase, produced by the microorganism Pseudomonasfluorescent IAM 1057. This lipase is available from Amano PharmaceuticalCo. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano,"hereinafter referred to as "Amano-P".

Especially suitable Lipase are lipase such as M1 Lipase (Ibis) andLipolase (Novo).

Peroxidase enzymes are used in combination with oxygen sources, e.g.percarbonate, perborate, persulfate, hydrogen peroxide, etc. They areused for "solution bleaching", i.e. to prevent transfer of dyes ofpigments removed from substrates during wash operations to othersubstrates in the wash solution. Peroxidase enzymes are known in theart, and include, for example, horseradish peroxidase, ligninase, andhaloperoxidase such as chloro- and bromo-peroxidase.Peroxidase-containing detergent compositions are disclosed, for example,in PCT Internation Application WO 89/099813 and in European Patentapplication EP No. 91202882.6, filed on Nov. 6, 1991.

In liquid formulations, an enzyme stabilization system is preferablyutilized. Enzyme stabilization techniques for aqueous detergentcompositions are well known in the art. For example, one technique forenzyme stabilization in aqueous solutions involves the use of freecalcium ions from sources such as calcium acetate, calcium formate andcalcium propionate. Calcium ions can be used in combination with shortchain carboxylic acid salts, preferably formates. See, for example, U.S.Pat. No. 4,318,818. It has also been proposed to use polyols likeglycerol and sorbitol. Alkoxy-alcohols, dialkylglycoethers, mixtures ofpolyvalent alcohols with polyfunctional aliphatic amines (e.g., such asdiethanolamine, triethanolamine, di-isopropanolamime, etc.), and boricacid or alkali metal borate. Enzyme stabilization techniques areadditionally disclosed and exemplified in U.S. Pat. No. 4,261,868, U.S.Pat. No. 3,600,319, and European Patent Application Publication No. 0199 405, Application No. 86200586.5. Non-boric acid and boratestabilizers are preferred. Enzyme stabilization systems are alsodescribed, for example, in U.S. Pat. Nos. 4,261,868, 3,600,319 and3,519,570.

Other suitable detergent ingredients that can be added are enzymeoxidation scavengers which are described in Copending European Patentaplication N 92870018.6 filed on Jan. 31, 1992. Examples of such enzymeoxidation scavengers are ethoxylated tetraethylene polyamines.

Other components used in detergent compositions may be employed, such assoil-suspending agents soil-release agents, abrasives, bactericides,tarnish inhibitors, coloring agents, and perfumes. In addition, it hasbeen found that the polyamine-N-oxide containing polymers eliminate orreduce the deposition of coloring agents onto fabrics resulting insubstantial no fabric spotting upon pretreatment and/or in the wash.

The liquid compositions according to the present invention can also bein "concentrated form", in such case, the liquid detergent compositionsaccording to the present invention will contain a lower amount of water,compared to conventional liquid detergents

Typically, the water content of the concentrated liquid detergent isless than 30%, more preferably less than 20%, most preferably less than10% by weight of the detergent compositions.

The present invention has found to be extremely useful when the liquiddetergents are in direct contact with the fabrics such as duringpretreatment. However, the present invention is also very suitable forinhibiting fabric spotting encountered during fabric launderingoperations.

The process of the invention can be carried out before or in the courseof the washing process. The washing process is preferably carried out at5° C. to 95° C., especially 20° C. to 60° C., The pH of the treatmentsolution is from 2 to 10.5, preferably from 3:5 to 10.5, more preferablyfrom 2 to 6.

The process and compositions of the invention can also be used aslaundry detergent additive products.

Typically, the laundry additive compositions contain no more than 10% byweight of a surfactant. The compositions according to the presentinvention have proven to be very useful when formulated in said laundryadditive compositions.

Such additive products are intended to supplement or boost theperformance of conventional detergent compositions.

The detergent compositions according to the present invention includecompositions which are to be used for cleaning substrates, such asfabrics, fibers, hard surfaces, skin etc., for example hard surfacecleaning compositions (with or without abrasives), laundry detergentcompositions, automatic and non automatic dishwashing compositions.

The following examples are meant to exemplify compositions of thepresent inventions, but are not necessarily meant to limit the scope ofthe invention.

A liquid detergent composition according to the present invention isprepared having the following composition:

                  TABLE I                                                         ______________________________________                                        % by weight of the total detergent composition                                                        (a)                                                   ______________________________________                                        Poly ethoxy propoxy alcohol                                                                           1.00                                                  Alkyl sulphate          1.00                                                  BHT (Butyl hydroxy toluene)                                                                           0.03                                                  Perfume (Miraflor)      0.10                                                  Hydrogen peroxide       7.00                                                  H.sub.2 SO.sub.4        to pH 4                                               Distilled water                                                               ______________________________________                                    

The extent of reduction on brightener spotting was studied underdifferent conditions corresponding to possible product usage conditionson 100% cotton fabrics. These product usage conditions were as follows:

I) Product applied on fabric for 10 minutes and then washed inlaundero-meter. (T: 40° C./washing time:25 min.)

II) Product dried on fabric and then washed in laundero-meter. (T: 40°C./washing time: 25 min.)

III) Product applied on fabric for 10 minutes and then rinsed

IV) Product dried on fabric and then rinsed

The fabric spotting was assessed by visual inspection of the samplesunder sunlight by a panel of expert graders, using the following scale.

    ______________________________________                                        psu 0       I am sure there is no brightener spotting                         psu 1       I seem to see a light spot but I am not sure                      psu 2       I am sure there is a light spot                                   psu 3       I am sure there is a spot                                         psu 4       There is a heavy spot                                             ______________________________________                                    

EXPERIMENTAL CONDITIONS

A: A detergent composition according to Table 1 which contains nobrightener and no poly(4-vinylpyridine-N-oxide)

B: A detergent composition according to Table 1 which contains 0.06% byweight of brightener (Tynopal CBS-X) and nopoly(4-vinylpyridine-N-oxide)

C: A detergent composition according to Table 1 which containspoly(4-vinylpyridine-N-oxide which has an average molecular weight ofabout 10 000 and an amine to amine N-oxide ratio of 1:5 (determined byNMR) and no brightener.

D: A detergent composition according to Table 1 which containsbrightener (Tynopal CBS-X and 0.06% by weight ofpoly(4-vinylpyridine-N-oxide) which has an average molecular weight ofabout 10 000 and an amine to amine N-oxide ratio of 1:5 (determined byNMR)

The results were as follows:

    ______________________________________                                                    A        B        C      D                                        ______________________________________                                        I           0        2        0      0                                        II          0        3        0      1                                        III         0        2        0      0                                        IV          0        4        0      2                                        ______________________________________                                    

As can be seen from the above results, brightener spotting issignificantly reduced by the addition of poly(4-vinylpyridine)-N-oxide.

The following laundry liquid detergent compositions were made:

    ______________________________________                                                          I      II       III  IV                                     ______________________________________                                        C.sub.12 -C.sub.15  Alkyl sulfate                                                               --     19.0     21.0 --                                     C.sub.12 -C.sub.15  Alkyl ethoxylated sulfate                                                   23.0   4.0      4.0  25.0                                   C.sub.12 -C.sub.14  N-methyl glucamide                                                          9.0    9.0      9.0  9.0                                    C.sub.12 -C.sub.14  fatty alcohol ethoxylate                                                    6.0    6.0      6.0  6.0                                    C.sub.12 -C.sub.16  Fatty acid                                                                  9.0    6.8      14.0 14.0                                   Brightener        0.1    0.1      0.1  0.1                                    N-vinylimidazole N-vinyl-                                                                       0.5    0.5      --   --                                     pyrrolidone copolymer                                                         Poly(4-vinylpyridine)-N-oxide                                                                   --     --       0.5  0.5                                    Hydrogen peroxide 5      5        5    5                                      Citric acid anhydrous                                                                           6.0    4.5      3.5  3.5                                    Diethylene triamine penta methy-                                                                1.0    1.0      2.0  2.0                                    lene phosphonic acid                                                          Water & Minors                                                                up to 100% - - -                                                              ______________________________________                                    

The above compositions (I-IV) were very good at displaying detergentperformance with excellent color-care benefits without creatingsignificant fabric spotting on the fabrics.

The following liquid laundry additives were made:

    ______________________________________                                                         (a)     (b)      (c)  (d)                                    ______________________________________                                        Dobanol ® 91-10                                                                            --      --       3    3                                      Dobanol ® 23-3                                                                             --      --       1    1                                      Dobanol ® 23-6.5                                                                           --      --       1    1                                      Lutensol ® A030                                                                            --      --       1    1                                      Poly ethoxy propoxy alcohol                                                                    1       1        --   --                                     Alkyl sulphate   1       1        --   --                                     BHT (Butyl hydroxy toluene)                                                                    1       1        --   --                                     Perfume (Miraflor)                                                                             1       1        1    1                                      Isofol 16        --      --       0.2  0.2                                    N-vinylimidazole N-vinyl-                                                                      0.3     --       0.3  --                                     pyrrolidone copolymer                                                         Poly(4-vinylpyrridine)-N-oxide                                                                 --      0.3      --   0.3                                    Brightener       0.06    0.06     0.06 0.06                                   Hydrogen peroxide                                                                              7       7        7    7                                      H.sub.2 SO.sub.4 to pH 4                                                      ______________________________________                                    

The above compositions (a)-(d) were very good at displaying detergentperformance with excellent color-care benefits without creatingsignificant fabric spotting on the fabrics.

I claim:
 1. A method of reducing brightener spotting comprising the stepof washing fabric with a composition comprising a polymer selected fromthe group consisting of polyamine N-oxide containing polymers,N-vinylimidazole N-vinylpyrrolidonedone copolymers and mixtures thereof,a stilbene brightener, and from 5% to 7% hydrogen peroxide, wherein theweight ratio of the polymer to the brightener is from 1:20 to 20:1 andthe pH of the composition is from 2 to
 6. 2. A method according to claim1, wherein the weight ration of the polymer to the brightener is from1:10 to 12:1.
 3. A method according to claim 2, wherein the weight ratioof the polymer to the brightener is from 1:1 to 12:1.
 4. A methodaccording to claim 3, wherein the weight ratio of the polymer to thebrightener is from 2:1 to 7:1.
 5. A method according to claim 1, whereinthe composition comprises from 0.001% to 10%, by weight, of a polyamineN-oxide containing polymer.
 6. A method according to claim 1, whereinthe composition comprises from 0.01% to 10%, by weight, of aN-vinylimidazole N-vinylpyrrolidone copolymer.
 7. A liquid compositioncomprising a polymer selected from the group consisting of polyamineN-oxide containing polymers, N-vinylimidazole N-vinylpyrrolidonecopolymers and mixtures thereof, a stilbene brightener, and from 5% to7% hydrogen peroxide, wherein the weight ratio of the polymer to thebrightener is from 1:20 to 20:1 and the pH of the composition is from 2to
 6. 8. A liquid composition according to claim 7, wherein the weightratio of the polymer to the brightener is from 1:10 to 12:1.
 9. A liquidcomposition according to claim 8, wherein the weight ratio of thepolymer to the brightener is from 1:1 to 12:1.
 10. A liquid compositionaccording to claim 9, wherein the weight ratio of the polymer to thebrightener is from 2:1 to 7:1.
 11. A liquid composition according toclaim 7, wherein the composition comprises from 0.001% to 10%, byweight, of a polyamine N-oxide containing polymer.
 12. A liquidcomposition according to claim 11, wherein the polyamine N-oxidecontaining polymer has a molar ratio of amine to amine N-oxide of 2:3 to1:1,000,000.
 13. A liquid composition according to claim 11, wherein thepolyamine N-oxide containing polymer has a molecular weight of from 500to 1,000,000.
 14. A liquid composition according to claim 11, whereinthe composition comprises from 0.01% to 10%, by weight, of aN-vinylimidazole N-vinylpyrrolidone copolymer.
 15. A liquid compositionaccording to claim 14, wherein the N-vinylimidazole N-vinylpyrrolidonecopolymer has a molecular weight of from 5000 to 1,000,000.
 16. A liquidcomposition according to claim 7, wherein the brightener isbenzenesulfonic acid,2,2'-((1,1'-biphenyl)-4,4'-diyldi-2,1-etheneidyl)Bis-, disodium salt.17. A liquid composition according to claim 7, comprising 0.06% to 0.1%,by weight, brightener.
 18. A liquid composition according to claim 7,comprising no more than 10%, by weight, surfactant.
 19. A liquidcomposition according to claim 7, comprising, by weight, from about 0.2%to about 40% anionic surfactant and from about 0.05% to about 40%nonionic surfactant.
 20. A liquid composition according to claim 7,comprising, by weight, from 0.1% to 1% polymer, 0.06% to 1% brightener,and 5% to 7% hydrogen peroxide, and having a weight ratio of the polymerto the brightener of from 2:1 to 7:1.